Alkyl diacetoxy-dimethyl-ring substituted-benzoates

ABSTRACT

The alkyl diacetoxy-dimethyl-ring substituted-benzoates of this invention have never before been recognized as perfumes or components thereof. They have different and more aggressive odor notes than the corresponding dihydroxy compounds. They may be successfully utilized to imitate or replace the scent of expensive natural oak moss products or odor notes of such products, making then especially useful perfume materials.

United States Patent Kulka Aug. 26, 1975 [75] Inventor: Kurt Kulka, New York, NY.

[73] Assignee: F ritzsche Dodge & Olcott Inc., New

York, NY.

[22] Filed: June 10, 1974 [2l] Appl. No.: 478,063

[52] US. Cl. 252/522; 260/473 R [5 I] Int. Cl. CllB 9/00; CO7C 69/78 [58] Field of Search 252/522; 260/473 R [56] References Cited UNITED STATES PATENTS 3,590,073 6/1971 Carr et al H 260/473 R 3,7S9 870 9/1973 Economy et al.... 260/473 R 3,855,274 l2/l974 Kato .i 260/473 R OTHER PUBLICATIONS Alexander Robertson et al., J. Chem. Soc. London. pp. 3038-304I, 1949.

Primary Examiner-Veronica OKeefe Attorney, Agent, or Firm-Frank M. Nolan 5 7 ABSTRACT The alkyl diacetoxydimethyl-ring substitutedbenzoates of this invention have never before been recognized as perfumes or components thereof. They have different and more aggressive odor notes than the corresponding dihydroxy compounds. They may be successfully utilized to imitate or replace the scent of expensive natural oak moss products or odor notes of such products, making then especially useful perfume materials.

7 Claims, No Drawings ALKYL DIACETO XY-DIMETHYL-RING SUBSTlTUTED-BENZOATES This invention relates to alkyl diacetoxy-dimethylring substitutedbenzoates and perfume compositions containing alkyl diacctoxydimethylring substitutedbenzoates.

In accordance with an aspect of this invention, one or more of certain alkyl diacetoxy-dimethyl-ring substitut' ed-benzoates may be employed in a perfume composi tion with one or more other odorous perfume components. One or more of the following alkyl diacetoxy dimethyl-ring substituted-benzoates may be employed for this purpose:

Methyl or ethyl 2.4-diacetoxy-3,o-dimethyl-benzoate Methyl or ethyl 2,6-diacetoxy-4,5-dimethyl-benzoate Methyl or ethyl 2,6-diacetoxy-3,S-dimethyl-benzoate Methyl or ethyl 4.6-diacetoxy-2.3 dimethyl-benzoate The methyl or ethyl diacetoxy-dimethyl-ring substituted-benzoates of the first six benzoates listed are new compounds. Methyl-4,6-diacetoxy-2,3-dimethylbenzoatc was reported by Alexander Robertson et al. in the Journal ofihe Chemical Society London, l949. pp. 3038-3041. However, neither this latter benzoate nor any of the other specified benzoates of this invention were disclosed or taught to be of any significance as 2 cals having one or more phenolic hydroxyl groups in their molecules.

The specified alkyl diacetoxy-dimcthyl-ring substitut ed-benzoates can be used in a variety of different per- 5 fume compositions The compositions may be incorpo rated in sachet powders. cosmetics such as soaps. creams body powders and other products such as household products to produce a desired perfume odor.

ln accordance with another aspect of this invention certain of the alkyl diacctoxydimethyl-ring substitut ed-benzoates which are novel compounds may be used in perfumes and for other purposes. such as flavor components. These novel alkyl diacetoxy-dimethyl-ring substitutcd-benzoates are:

Methyl 2 4-diacetoxy-3.o-dimethyl-benzoate Ethyl 2 4-diacetoxy-3,fi-dimcthyl-benzoate Methyl 2,6-diacetoxy-4 S-dimethyl-benzoate Ethyl 2,6-diacetoxy-4.5-dimethyl-benzoate Methyl 2,6diacetoxy-3,5 dimethyl-benzoate Ethyl 2,6-diacetoxy-3,S-dimethyl-benzoate The alkyl diacetoxydimethyl-ring substitutedbenzoates are produced by reacting acetic anhydride with the required alkyl dihydroxy-dimethyl-ring substitutcd-benzoate in accordance with the following scheme:

aroma chemicals in perfumery.

The total amount of the alkyl diacetoxy-dimethylring substituted'bcnzoate or a mixture of such benzoates is at least 1% by weight. desirably l to and preferably 2 to 5% by weight.

Desirably. the other perfume component or components comprise in their entirety l to 99% by weight of the total perfume composition.

For the production of the perfume compositions of this invention, one or more of the specified alkyl diacetoxydimethyl-ring substituted-benzoates are uniformly mixed with one or more of the other perfume components. The specified alkyl diacetoxy-dimethyl-ring substituted-benzoates enhance and/or modify the odors of the perfume compositions. They have significantly ag gressive odor notes and are employed to imitate or re place expensive natural oak moss products or odor notes found in such natural products. The alkyl diacetoxy-dimcthyl-ring suhstituted-bcnzoates employed in the perfume compositions of this invention do not become discolored on standing or when incorporated into perfume compositions or cosmetics. as do other chemiin which R is methyl or ethyl.

The required alkyl dihydroxy-dimethyl-ring substituted-benzoate may be methyl 2.4-dihydroxy-3,6- dimethyl-bcnzoate. ethyl 2,4-dihydroxy-3.6-dimethylbenzoate, methyl 2,o-dihydroxy-4,5-dimethylbenzoatc, ethyl 2,6-dihydroxy-4,S-dimethyl-benzoate, methyl 2.6-dihydroxy-3,S-dimethyl-benzoate, ethyl 2,- 6-dihydroxy-3,5-dimethyl-benzoate, methyl 4.6- dihydroxy-Z.3-dimethyl-benzoate and ethyl 4,6- dihydroxy-2.3dimethyl-bcnzoate. The parent chemicals from which the six specified novel alkyl diacetoxy dimethyl-ring substituted-benzoates are derived are listed in Beilsteins HANDBUCH DER ORGANSC- HEN CHEMlE, Vol. l0.

Desirably. a small excess of acetic anhydride is employed. for example. a molecular ratio of 1 mol of the alkyl dihydroxydimcthyl-bemoatc to 2% mols of acetic anhydridc. Preferably, the reaction is conducted in the presence of a solvent such as xylene which forms an aleotrope with acetic acid.

The formed azeotrope is removed by distillation as it is formed through a fractionation column such as a Vireux column. After completion of the reaction. the iert solvent and excess anhydride are distilled off in an iector vacuunL lf purification is desired. the reaction roduct is dissolved in a suitable inert solvent such as enzene. The resulting solution is washed with water. )dium bicarbonate solution, and finally with water. If esired. it is rectified by recrystallization from an apropriate solvent such as isopropanol.

A more comprehensive understanding of this invenon is obtained by reference to the following examples:

EXAMPLE I Methyl 2,4-Diaeetoxy 3,o-dimethyl-benzoate One mole of methyl 2,4-dihydroxy-3.o-dimethylenzoate is combined with 2-1/2 mols of acetic anhyride and 200 ml ofxylene. The formed azeotrope conisting of acetic acid and xylene, boiling at l l5-l l6C. removed as it is formed by distillation through a 1 ft. igreux column. After completion of the reaction. the xcess acetic anhydride and xylene are distilled off in n ejector vacuum. The remaining crude reaction prodct is dissolved in 200 ml of benzene. The resulting so- Jtion is washed successively with water. sodium bicaronate solution. and again with water. The methyl 2,4- .iacetoxy-3,6-dimethyl-benzoate may be rectified if lesired by recrystallization from a solvent such as iso iropanol.

If it is desired to produce any of the other alkyl diaceoxy-dimethyl-benzoates utilized in the practice of this nvention, one mol of the required alkyl dihydroxylimethylbenzoate may be employed instead of the nethyl 2.4-dihydroxy-3,fi-dimethyl-benzoate of this eximple. For instance, if ethyl 2,4-diacetoxy-3,6- limethyl-benzoate is desired. it may be obtained by :mploying one mol of ethyl 2,4-dihydroxy'3.6 limethyl-benzoatc instead of the one mol of methyl 2,- l-dihydroxy-3.o-dimethyl-benzoate and then following he procedure of this example.

EXAMPLE ll aehet Powder Containing One or More of the Novel \lkyl Diacctoxy-Dimethyl-Ring Substituted-Benzoates as the Only Perfume Component A sachet powder containing no perfume component )ther than one or a mixture of two or more of the six lOVCl alkyl diacetoxy-dimethyl-ring substituted- )enzoates of this invention may be prepared by inti nately mixing:

50 parts of one or a mixture of different novel alkyl methyl(or ethyl)diacetoxy-dimethyl-ring substituted-benzoatcs 50 parts of talcum powder or kaolin or any diatomaceous earth.

In this example, any one or a mixture of the following iovel alkyl diacetoxy-dimethyl-ring substituteduenzoates may be used totaling 50 parts by weight:

Methyl 2.4-diacetoxy-3.6dimethyl-benzoate Ethyl 2.4-diaeetoxy-3.e-dimethyl-benzoate Methyl 2.6-diacetoxy-4.5-dimethyl-benzoate Ethyl 2.6-diacctoxy-4,5-dimethyl-benzoate Methyl 2 6-diacetoxy-3.5dimethyl-benzoate Ethyl 2,6diaeetoxy-3,S-dimethyl-benzoate In this example and in all examples which follow. all Jarts of components and ingredients are by weight.

EXAMPLE lll Musk Sachet Powder A musk sachet powder is produced by intimately mixing together;

parts of one or a mixture of alkyl diaeetoxydimethyl ring substitutcd-benzoates as specified in this example 10 parts of synthetic musk. such as:

Versalide: l.l .4.-1-tetramethyl-fi-ethylJ-acetyll.13.4-tetrahydronaphthalene; or

Celestolide: 4-aeetyl-l .l-dimethyl-o tert.butylindan; or a nitro-musk such as musk ketonc. musk xylene ln this example, any one or a mixture of the following alkyl diacetoxy-dimethyl-ring substituted-benzoates may be used totaling 90 parts by weight of:

Methyl 2.4-diacetoxy-3.o-dimethyl-benzoate Ethyl 2.4-diaeetoxy-3.o-dimethyl-benzoate Methyl 2,6-diacetoxy4.5-dimethyl-benzoate Ethyl 2,6-diacetoxy-4,5-dimethyl-benzoate Methyl 2 6-diacetoxy-3.5-dimethyl-benzoate Ethyl 2.6-diacetoxy-3.S-dimethyl-benzoate Methyl 4.o-diaeetoxy-2,3 dimethyl-benzoate Ethyl 4.6-diacetoxy-2 3-dimethylbenzoate EXAMPLE IV Phantasy Type Perfume Composition A phantasy type perfume composition is produced by mixing together:

I25 parts of one or a mixture of alkyl diacetoxydimethyl-ring substituted-benzoates as specified in Example lll 300 parts of oil geranium 200 parts of oil ylang ylang I00 parts of heliotropin I00 parts of vanillin 25 parts of iso-eugenol 50 parts of a-amyl-cinnamic aldehyde 50 parts of oil patchouly 30 parts of phenylethyl alcohol 20 parts of orange flowers absolute EXAMPLE V New Mown Hay Type Perfume Composition A new mown hay type perfume composition is produced by mixing together:

20 parts of one or a mixture of alkyl diacetoxydimethyl-ring substituted-benzoates as specified in Example Ill 50 parts of dimethyl hydroquinone 200 parts of oil lavender 250 parts of linalyl acetate 50 parts of methyl salicylate l0 parts of oil clary sage 50 parts of oil ylang ylang 30 parts of tonka bean absolute 10 parts of oil patchouly 5 parts of oil vetivcrt 50 parts of linalool l0 parts of benzyl acetate 200 parts of hydroxycitronellal 5 parts of diphenyl oxide 30 parts of coumarin l0 parts of vanillin 20 parts of musk ketone Fougere l'ypc Perfume Composition EXAMPLE \'I 120 parts of oil ylang-ylimg bourbon 80 parts of oil geranium l0 parts parts of oil patchouly of oil vetivert I00 parts of vanilla extract 60 parts 30 parts of, o ionone of amyl salicylate 5 parts of oil tarragon 150 parts of phenylethyl alcohol 170 parts of a amylcinnamie aldehyde 50 parts 30 parts parts Chyprc Type Perfume Composition of coumarin of musk ketone of heliotropin EXAMPLE Vll A chypre type perfume composition is prepared by mixing together:

(at) parts of one or a mixture of alkyl diacetoxydimethyl-ring substituted-benzoatcs as specified in Example ll] parts l5 parts l2 parts to ptlt'lS fit] parts 80 parts 1() parts It) parts of coumarin of oil putchouly of oil vetivcrt of oil sandalwood of linztlkyl acetate of oil cedarwood of i'anillin of musk ketonc 5 parts of phenylethyl alcohol 7 parts of resinoid ltibdunum What is claimed is:

l. A perfume composition comprising at least Hi by weight of an alkyl diucetoxy-tlimethyl-ring substitutedbcnzoate and F99) by weight of an odorous perfume component. said alkyl diacctoxy-dimethybring substituted-ben/oate being selected from the class consist ing of methyl 2.4-diaeetoxy3.o-dimethyl-benzoute. ethyl 2.4-diacetox -3.b-dimethyl-benzoate. methyl 2.6- diatcetoxy-4.5-dimethyl-bcnzoatc. ethyl 2.(diaeetoxy- 4.5-dimethyl-benzoate methyl 2.6-diacetoxy-3.5- dimethyl-benzoate. ethyl 2.o-diucetoxy-3,5-dimethylbenzoate. methyl-4.64iacetoxy-2.3-dimethyl-benzoate and ethyl 4 6-diacctoxy-Z.3-dimethyl-benzoate.

2. A perfume composition of claim 1 in which the alkyl diucctoxy-dimethyl-ring substituted-benzoate comprises l to 30% by weight of the perfume composition.

3. A perfume composition of claim 1 in which the alkyl diucetoxy-dimethyl-ring substituted-benzoate comprises 2 to 5% by weight of the perfume composition.

4. A perfume composition of cluim in which the alkyl diucetoxy-dimethyl-ring substituted-benzoate is methyl (or ethyl) 2.4-diacetoxy-3.6-dimethylbenzoate.

5. A perfume composition of claim 1 in which the alkyl diacetoxy-dimethyl-ring substituted-benzoate is methyl (or ethyl) 2.6-diucetoxy-4.5dimethyl benzoute.

6. A perfume composition of claim I in which the alkyl diacetoxydimethyl-ring substituted-bcnzoute is methyl (or ethyl) lfi-diacetoxy-3,S-dimethylbenzoute.

7. A perfume composition of claim I in which the alkyl diacctoxy-dimethyl-ring substituted-benzoate is methyl (or ethyl) 4.6-diacetoxy-2.3 dimethylbenzoate. 

1. A PERFUME CONPOSITION COMPRISING AT LEAST 1% BY WEIGHT OF AN ALKYL DIACETOXY-DIMETHYL-RING SUBSTITUTED-BENZOATE AND 1-99% BY WEIGHT OF AN ODOROUS PERFUME COMPONENT, SAID ALKYL DIACETOXY-DIMETHYL-RING SUBSTITUTED-BENZOATE BEING SELECTED FROM THE CLASS CONSISTING OF METHYL 2,4-DIACETOXY-3,6DIMETHYL-BENZOATE, ETLYL 2,4-DIACETOXY-3,6-DIMETHYL-BENZOATE, METHYL 2,6-DIACETOXY-4,5-DIMETHYL-BENZOATE, ETHYL 2,6DIACETOXY-4,5-DIMETHYL-BENZOATE, METHYL 2,6-DIACETOXY-3,5 DIMETHYL-BENZOATE, ETHYL 2,6-DIACETOXY-3,5-DIMETHYL-BENZOATE, METHYL-4,6-DIACETOXY-2,3-DIMETHYL-BENZOATE AND ETHYL 4,6-DIACETOXY-2,3-DIMETHYL-BENZOATE.
 2. A perfume composition of claim 1 in which the alkyl diacetoxy-dimethyl-ring substituted-benzoate comprises 1 to 30% by weight of the perfume composition.
 3. A perfume composition of claim 1 in which the alkyl diacetoxy-dimethyl-ring substituted-benzoate comprises 2 to 5% by weight of the perfume composition.
 4. A perfume composition of claim 1 in which the alkyl diacetoxy-dimethyl-ring substituted-benzoate is methyl (or ethyl) 2,4-diacetoxy-3,6-dimethyl-benzoate.
 5. A perfume composition of claim 1 in which the alkyl diacetoxy-dimethyl-ring substituted-benzoate is methyl (or ethyl) 2,6-diacetoxy-4,5-dimethyl-benzoate.
 6. A perfume composition of claim 1 in which the alkyl diacetoxy-dimethyl-ring substituted-benzoate is methyl (or ethyl) 2,6-diacetoxy-3,5-dimethyl-benzoate.
 7. A perfume composition of claim 1 in which the alkyl diacetoxy-dimethyl-ring substituted-benzoate is methyl (or ethyl) 4,6-diacetoxy-2,3-dimethyl-benzoate. 